Dyestuffs containing metals and process of making same



Patented July 5,1932

UNITED v STATES FRITZ STRA'UB AND WALTER ANDERAU, 0F BASEL, SWI'IZERLAND, ASSIGNOBiS TO 1 FIRM SOCIETY OF CHEMICAL INDUSTRY IN BASLE, 0E BASEL, SWITZERLAND nxns'rurrs conrArNIne METALS nnrnocnss or MAKING sAiuE No Drawing. Application filed July 5, 1929, ser al No. araarefand n Switzerlandl'uly 13,1928.

This inventionrelates to the manufacture of new dyestuffs containing metals. It cornprises the process of making these dyestuiis, the dyestuffs themselves and the material that has been dyed with the new products.

The invention is based on the observatlon that remarkably fast dyeing products are obtained by treating azo dyestuifs of the general formula 1 dyestuffs and'to polyazo-dyestuifs, irrespective of the number-of atomlc grouping capable of forming lakes. As groups capable of forming lakes there come into consideration hydroxyl and carboxyl groups which stand in ortho-position to the N=N- bridge, as well as the ortho-hydroxyl-carboxyl group.v The compounds of. various metals which may form complexes may beused as agents yielding metals, such as compounds of copper, chromium, nickel, cobalt, titanlum, iron, tin, aluminium, or the like, and the complexes may contain one or more metals. As

to the oxidizing agent, this also may vary greatly; among others, there have proved particularly useful chlorine (for instance, in the form'of hypochlorite), atmospheric oxygen, chromic acid and its salts, hydrogen peroxide and compounds thereof, potassium ferricyanide, or the like, as well as the electrolytic oxidation. 1 v

The process may be conducted in'any desired sequence. The sodium salts of the color acids may be treated with oxidizing agents and the oxidized dyestuffs thenmetallized, or

else the complex metal compounds may be oxidized. As a whole theproperties ofthe,

products obtained according to these two methods are identical, butfaccording to the conditions under which the oxidizing agent acts, small difi'erences maybe observed. Y

Particularly valuable have proved to bathe products which are derived from diazotized :tized aminonaphthol sulfonic acids, etc., and

in substance but in the dye-bath ortho-hydroxy-amino-compounds of the henzene and naphthalene series, such as diazotized .chloroaminophenols and nitroaminophenols and the sulfonic acids thereof, diazothe 2 amino 5 hydroxynaphthalene-7-sul- ,fonic acid as coupling component.

The new dyestuffs may be made not only or on the fiber'or in a printing operation. r The following examples illustrate the in Vention, the parts being by weight 7 i Ewample 1 g In a solution alkaline with sodium carbonate, the diazo compound from 223.5 parts of eL-chloro-Q-a'mino-l-phenol-6-sulfonic acid are coupled with 239 parts of 2-amino-5-hyv droxynaphthalene-Wsulfonic acid. When coupling is completed, the whole is warmed and there is added anammoniacal copper oxide solution made from 250 parts of crystallized copper sulfate, whereupon the blue-red color of thecopper compound is formed' By evaporation and prolonged drying ofthe dyestufithere is obtaineda new dyestufi' which dyescotton and artificial silk fast grey tints in a bath which is neutral or alkalinewith sodium carbonate or caustic alkali. Thedyestuff may be purified by re-precipitation. By

addition of glycerine or the like. or of; an oxygen carrier the process of the formation of thedyestuff may be favored, 1

. ,Ewample? i v The copper compound ofthe azo-dyestufi from eL-cholor-Q-amino-l-phenol-6-sulfonic f acid and .Z-a-mino-5-hydroxy-naphthalene-7- sulfonic acid is dissolved by'addition of ammoniav to forma hot solution of 6 per cent.

strength; Through thislsolution a current of air is passed for some time, whereby the original compound which dyes redviolet, is

converted into onewhich dyes grey. By increasing the temperature. and by adding an oxygen carrier, such as a copper salt or-a vanadium compound, the process may be accelerated. The product is worked up in the usual manner. v The. oxidation with air may'also be effected at the boiling temperature without the addi tion of catalysts. v The oxidation of the metalcompounds of the azo-dyestuffs may occur under pressure at a temperature above 100 C. i

' 'Ewample3 I 47.4 parts of the azo-dyestufl? from chloro-2 amino-l-phenol-G-sulfonic acid and- 2 amino 5 -hydroxynaphthalene -7 esulfonic acid are converted'intothe coppercompound in known manner and the latter is dissolved in 1200 parts of hot water by addition of -5,7 partsof caustic soda solution. By adding 10019.0 parts of potassium'ferricyanide there is produced, 'aftersome time, from the red- -violet parent dyestufl? thenew dyestuff which fdyesfast grey tints'andmay be separated in the usual manner by salting out.

. Instead .of potassium ferricyanide there I may be used with like result a corresponding proportion of an alkali perborate, alkali persulfate or lead peroxide.

7 Ezramplelt Y v V The quantity of the azo-dyestuff from diazotized nitrate'd 1-amino-2-naphthol-4- sulfonic acid and Q-amino-5-naphthol-7-sulfonic acid, corresponding with 70 parts of sodium nitrite, is dissolved in 1200 parts of water, andthe solution is mixed with'one of chromium 7 fluoride corresponding with 150 parts of Cr O by boiling the whole in a reflux apparatus for 15-20 hours, the chromium compound which dyes green is'pro duce-d. The whole is'made alkaline with sodium car- 'bonate and filtered from the mudof chros'o' verted into zinc compound by addition of (a solution of sod um zincate made from 28L? mium' compound and then mixed with potassium hypochlorite, corresponding with 100- 200 'parts 'ofactive chlorine to produce the new compound. By concentration and salting out, there is obtained a blackishpowder wliich dyes silk and wool fast green tints in an-acid bath;

Instead of metal compounds which contain only one metah'there maybe used metal compounds of azo-dyestu-ffs'which contain several metals. 7

Example j 47 part s of the azo dystuff from l-chloro- 2-amino-1-phenol-6-sulfonic acid and 2- amino-5-hydroxynaphthalene-7-sulfonic acid are dissolvedin 1000 parts of water and conparts of crystallized zinc sulfate and 20 parts 'ofcaust'ic soda solution of 36 B. Y Onaddition of 105 orniore parts of active chlorine in the form of alkali hypochlorite, the color of the alkali-solution changes from blue-red towardsblackyiolet. The :z-inc compound -ca-n beisolated as usual by neutralizing and adding common salt.

"Ewample6 I The quantity of the ortho-oXyazo-dyestuff from diazotized 2- amino 1-phenol-4 6-disul- 'fonic acid and 2-amino-5-hydroxynaphthalene-7 sulfonic acid, which corresponds with 7 partsof'sodlum n1tr1te,1s converted in known manner into the copper compound and this is dissolved in 1000 parts of water and made acid by means of 18 parts of acetic acid. There are now added,by degrees, at a slightly raised teniperature8-15 parts of potassium bichromate and the whole is stirred for some .time. ,The color passes. from violet to grey.

is diluted withfiwatertov itimes its volume and oxidized with 15001 moreparts of active chlorine in the .form of an alkali hypochlorite accompaniedrby slight heating. The dyestuif is dark brown-violet in alkaline solution and brown-orange in acetic acid solution, .in concentrated sulfuric acid it dissolves/to a blackish solution. It dyes cotton in a bath alkaline with sodium carbonate grey tints. which becomea grey fast to acids and light by an after-treatment with a copper salt. The solution is then acidified slightly with acetic acid and by addition of 250 parts of copper sulfate in the form of a concentrated solution, the dyestu'fi isconverted into the copper compound. From the adding common salt and purified by recrystallization. There is thus obtained a blackish powder which dissolves in water and dilute alkalies to a grey solution and in concentrated sulfuric acid to a greenish-blue solution; it dyes fiber fast greenish-grey tints. r V Example-8' From the violet copper compounds of the dyestuffs indicatedby the following schemes, fast grey tints can be developed in the dyebath in presence of an oxidizing agent: v

4-chloro-2-amino-1-pheno1-6-su1fonic acid-a 2-amino-5-hydroxynaphthaleneJ-sultonic acid 4-nitro 2-amino-1-pheno1-6-su1fonic acid'- do. 2-aminoJ-phenoM-sulfonic acid do.

iFor 10 parts of cotton there is prepared "a dye-bath from 400 parts of water, 0.3 part of copper compoundand 0.3-1 part of potassium ferricyanide or the like quantity of hydrogen peroxide solution of 25 per cent. strength, and 05. part or more of sodium carbonate.

salt or Glaubers salt amounting to 1 2 parts.

The goods .are then rinsed hot and lightly The goods are entered at 2030 C. and the bath isgradually heated to boiling {and gently boiled for to 1 hour. At half time, it is advantageous to add some common heated solution the latter is precipitated by soaped. Reddish-grey to greenish-grey tints 1:5

are obtained having excellent properties oi The metal compounds of the az'o-dyestuffs serving as parent materials in' the foregoing examples can be developed to fast grey tints and fixed by printing them and subsequently steaming in the presence of an oxidizing agent. V

For the manufacture of the printing paste, 5 parts of the complex metal compound of per cent. strength is madeinto a paste with 20. parts of water, and this "paste is mixed in the usual manner with 60 parts of starch tragacanth thickening, 5 parts of so.- dium chlorate of 40 percent. strength and 10 parts of Water. After printing, the; goods are steamed for hour under atmosphere pressure and thens'o apediz i l some other oxidizing agent.

Example 10 100 parts of wool are thoroughly wetted in 2000 parts of water in the usual maimer. 2 parts of the dyestufi made as described in Example 4 are dissolved in 10 15 times their weightof boiling water and addedto the dye-bath heated'to C. After addition of one-third of the necessary proportion of acid and 10 per cent. of Gla-ubers salt, the goods are entered and the bath brought to the boil and boiled for20 minutes to half an hour. A second third part of theacid is then added and the boiling continued for 20-30 minutes, whereupon'the remainder of the acid is added and boiling again continued for hour. 7

In all, 9 parts of sulfuric acid are neces- Instead of sodium chlorate, db parts of potassium ferricyanide of 40' per, cent. strength or copper acetate may be used, or

'After rinsed. r

. .Eammnplell.

' parts of silk are thoroughly Wette in 2000 parts of water-inthe usual manner. Therelare then addedfto the dye-bath, heated to 60 C., 4 per centofaceticacid of 40 per dyeing, the goods-are thoroughly 1 cent.strength, 2 partsofthe'dyestufi madeas' 0 described in Example 2 dissolved in 10-15 times its weight of hotwater; the goods are entered'and' dyeing is continued for A of an hour at 60 C. after, which the temperature is raised to '80-85 C. and a further 2-4=per cent. of acetic-acid of 40 per cent. strength 0 isadded,-and dyeing is continued for onehalf tothree-qu'arters of an hour at the lastnamed temperature. rinsed and dried. p Ema wiple lfl 100 parts of well boiled out or The goods are: then thoroughly "wetted cotton are dyed in'a dye-bath containadded 2 parts of the dyestufi made as pre of the bath is raised to boiling in thecourse of hourythere are then added to the ,dye-bath-25-30 parts of Glaube'rs salt and the goods are handled at the boiling temperature The goods are then washedand dried. j Itis also possible to dyein a feebly'alkaline "or feeblylacidbath. w

In the following" table "aref i'vn furtherexamples of lmetalliferous. dyestuffs which can be converted into individual products by sary. treatment with hypochlorite: f I

v Tintiofthe Tintotthe Metal Diazoti zing component Coupling component 7 5 2 625 gggg gd r product 7 dyestufi 1. Cu 4-ch1oro-2-amin0-1-phenol-6-sulfonie acid Earning-5 l1yidroxynaphtha1ene-7-su]- Blue-rein..- B1ue-greyi omc ac! 2. 'd0 .Q ;.do d0- Grey. 3. Sulfa-amido-salicylic acid "510.... 'Dp. 4. 2-amino-l-phenol-4-sulfonic aciddo, d Reddish-grey. 5. 4-nitro-2-aminor1-phen01; -do Red grey. 6. 4-nitro-2-amino-l-phenol-fi-sulfonic acid -do Green-grey. 7. Nitratedd1-diazo-2-hydroxynaphthaleneA-suliodo Blue-green.

nlc acl x I v p 8. 2-diaso-1-hydroxynaphthalene-4: S-disulfonic do;; Blue. ac1.' 9. 4-chloro-2-amin0-1-phenol-6-sulfonie acid 2-2;.mino- 8:gydroxynaphthalene-fi-su1 Grey,

0111c aci 10. Anthranilic acid 2-amino-5-hydroxynaphthalene-Fsul{ j' V Brown-grey.

' i' ionic acid. 2 V 11. 5-nitro-2-amino-1-pheno1 do Blue-green, 12.. 4-chloro-2-amino -1-pheno1-6-sulfonicacid Blue-v olet Grey-blue. 13. Sulio-amido-salicylic acid.' 7 I iolet Redrey. 14. 2-amino-1-phen0l-4-sulfonic'acid -d0 Blue-grey. 15. 4-nitro-2-amino-l-phenol-fi sulfonie acid" Blue-v1olet Green-blue. 16. 2-arniio-1-hydr0xynaphthalene-4: 8-(1 i s 111 1' o 11 ie p Blue Do. aci. p 17. Azo-dyestuff from 4-chlofo-Z-amino-l-phenoLG- l do Grey.

sulfonic acid-- 2-amino-S-hydroxynaphthalene- 7-sulf0nic acid (alkaline). j V 18. Cu 5-nitr0-2-amino-1-pheno1z. 2-amino-5-hydroxynapl1thalene-lz7 do Blue-grey. i' V d sul on aqi I. f

scribed in Example'h, dissolved in 10-15 times their. weightofhot water. The goods are enteredat20-25 C. and the temperature ing 2500 parts of water, toswhich have been 1. Process for the manufacture of new dyestufi's containingimetals, consisting in treating azo-dyestufi's of the general formula wherein one of the ws stands for hydrogen 7 wherein one of the ms stands for hydrogen r and the other m for an NH egroup, and

wherein R means an aromatic radicle of any diazo compound wh1ch carries in OIthO-POSltion to the N=N bridge a group capable of forming lakes, in'any desired sequence with oxidizing agents and with agents yielding metals of the atomic weight ranging between 748.1 and 65.4.Vwhichvare capableofforming complexes. V

3. Process for the manufactureof new dyestufls containing metals, consisting-in treati 7 ing azo-dyestufis of the general formula position to the -N=N group a group oapable of forming lakes, in any desired sequence with oxidizing agents and with agents yielding metals of the atomic weight ranging forming complexes, 7

ing azo-dyestufis ofthe general formula HOaS position to the N=N-- group a hydroxyl group, in any desired sequence oxidizing agentsand :withiag'ents yielding-metals of the atomic weight ranging between 52.1.and

63.6 which arecapableof forming complexes. v 5. Process for the manufacture of new dyestuflscontaining metals, consisting in treating "azo-dyestuffs of the general formula wherein R stands for a radicle of the phenyl series which carries in ortho-position to the -N=.N" (group a hydroxyl group, with agents yiel ing copper and with oxidizing agents." i

SOaH" V agents yielding copper andwith sodium .hypochlorite.

7. As new products the dyestuffs containing metals which, are obtainedeb'y treating aze-dyestuffs oft he" general formula Y I V hHOlS- I L as,

wherein" one of thefws stands for hydrogen and the other as for an NH -group, and wherein R means an aromatic radicle of any 7 diazo-compound which carries a group capable of forming lakes, in any desired sequence with oxidizing agents and with agents A yielding metals which are capable of forming. complexes, which products form dark powders which dye cotton and artificial silks fast green-grey to red-grey, blue-green, browngrey and grey tints.

V '8. As new products the dyestuffscontaint 52.1 d n 7 101 ing metals WhlCll are obtained'by treating be Ween an 63 6 We i am qtpa Q 9 azo-dyestufis of the general formula 4. Process for the manufacture ofnew dye- V i Y stufit's containing'metals, consisting in treat- 7 wherein one of the ms" stands for hydrogen and the Other x for a NH -group, and wherein 7R means an aromatic radicle of any diazo compound which carries in ortho-position to the -N=N- bridge agroup capable of forming lakes, in any desired sequence with ox n ,ag i s nd wit g ts in metals of the atomic weight ranging between 48.1 and 65.4 which are capable of forming complexes, which products form dark po-wders which dye cotton and artificial silks fast green-grey to red-grey, blue-green, browngrey and grey tints.

9. As new products the dyestuffs containing metals which are obtained by treating azo-dyestulfs of the general formula HOaS- NH:

wherein R stands for an aromatic radicle of any dlazo-compound whlch carrles 1n orthoposition to the -N=N group a group ca-- pable of forming lakes, in any desired se'' quence with oxidizing agents and with agents yielding metals of the atomic weight ranging between 52.1 and 63.6 which are capable of forming complexes, which products form.

dark powders which dye'cotton and artificial silks fast green-grey to red-grey, blue-green, brown-grey and grey tints. Y 10. As new products the dyestuffs containing metals which are obtained by treating azo-dyestufls of the generalformula I OH wherein R stands for an aromatic radicle of any diazo-compound which carries in ortho-position to the N=l l group a hydroxyl group, in any desired sequence with oxidizing agents and with agents yielding metals of the atomic weight ranging between 52.1 and 68.6- which are capable of forming complexes, which products form dark pow ders which dye cotton and artificial silks fast green-grey to red-grey, blue-green and grey tints. a A

' 11. As new products the dyestuffs containing metals which are obtained bytreating azo-dyestufl's of the general formula wherein R stands for a radicle of the phenyl powder which dyes cotton and artificial silks fast grey tints.

In witness whereof we have hereunto signed our names this 24th day of June, 1929.

FRITZ STRAUB.

WALTER ANDERAU'.

series which carries in ortho-position to the A N=N group a hydroxyl group, with agents yielding copper and with oxidizing agents, which products form dark powders which dye cotton and artificial silks fast green-grey to red-grey, blue-green and grey tints. 7

12. As a new product the dyestuff contain- 

